Dyestuffs of the anthraquinone series



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Patented Oct. 18, 1938 2,133,274 DYESTUFFS OF THE 'ANTHRAQUINONE SERIES William Dettwyler, Milwaukee, Wis., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application May 25, 1936, Serial No. 81,687

4 Claims. (Cl. 260-276) This invention relates to the preparation of tend to give deeper (bluer) shades of red, while new dyestuifs of the anthraquinone series, and those of high molecular weight give yellower more particularly to the preparation of the conshades. The following list of condensation proddensation products of 3-amino-anthraquinoneucts is given to illustrate the broad scope of ap- 5 2,1(N) -benzacridone with organic acid chlorides, plicants invention, all of which dye cotton in and their halogenation products. The invention varyingshades of red: 7 has for its object the preparation of new dye- Stufis of the anthraquinone-aclidone Series Acid chloride condensed with 3-ainino-anthra- 00101. in H250 which dye cotton in deeper and more desirable Nwenmndme 10 shades than are obtained from the unsubstitutv ed mp unds of this series, and which have good -naphlthglyl ctlliloride Redggown. fastnesspropertieslithm-fifiniraittaiatia;a;."::::::::::::: Brown.

I have found that 3-amino-anthraqujnone- Anthrathiazole-Zcarbonyl chloride Yellow brown- 2,1(N) benzacridone (obtainable by the amida Aiciltllliglaitginone-zl-benzacndone-para-carbonyL. Red brown.

15 tion of a 3-halogen-anthraquinone-2,1(N)-benz- Terephthaloyl chloride acridone, as more particularly described in cooxalyl'chlonde pending application Serial No. 28,141), may be condensed with organic acid chlorides to give Example 2 dyestufis which dye cotton in fast red shades- I Prior to the isolation of the product of Exam- 20 have also found that by the introduction of halop19 1 from th ortho-dichlorobenzene solution, gen in these new substituted anthraquinone- 50 parts f cetic acid and 20 parts of sodium a d n dy s s l s are a d which acetate (anhydrous) may be added, and chlorine have increased tinctorial strength. The halogen passed into the solution at C. until one may be introduced either before or after the conmolecular t t for each mole f 3 a densation effectedanthraquinone-2,1(N) -benzacridone originally The following eXampleS e given m fully used has been absorbed. The resulting 4-chloroillustrate the invention. The parts used are by 3-benzoylamino-anthraquinone-2,1(N) -benzac- W h ridone may be isolated as in Example 1. It dyes Efwmple 1 cotton in stronger shades than the non-chlor- 30 10 parts of 3-amino-anthraquinone-2,1(N)- mated product'- benzacridone and 5 parts of benzoyl chloride are Example 3 heated in 250 parts of orthodichlorobenzene at 10 parts of 3-benzoy1amino-anthraquinoneb u o a pe od Of 2 0 3 s, 2,1(N) -benzacridone as prepared in Example 1 33 til no free amino-anthraquinone-benzacridone e suspended in 50 parts of nitrobenzene. 5

' remains. The reaction mass is cooled to room parts f odium acetate and 50 parts of acetic empe a r a d t e e 0y acid are added. The mass is heated to 100 and qui O d filtered Off, WaShed chlorine gas is passed into the solution until 3 with ortho-dichlorobenzene, then with alcohol,- moles of chlorine have been absorbed. The new A0 and dried- When dry it is a r d DOWder 501111916111 trichloro 3 benzoylamino anthraquinone 2,1

* concentrated sulfuric acid with a brown red color )..b id e thus obtained is a dark red d Soluble in o O a c So v ts W th a red powder, soluble in concentrated sulfuric acid color. It dyes cotton from a violet hydrosulfite' with a red brown color. It dyes cotton instrong vat in fast red shades. red shades.

45 I found that acylation of 3-amino-anthraqui- Example 4 none-2,1(N)-benzacridone in all cases gives dye- 10 parts of a dibrommated 3 amino anthra stufis which dye in red Shades, Varying from quinone-2,1 (N) -benzacridone obtainable by the lowish to brownish red, depending on the bromination of 3-amino-anthraquinone-2,l(N)

. ticular acid chloride used. It is found that in benzacridone, as more particularly outlined in 50 general the acid chlorides of low molecular weight oopending application Serial No. 28,141, are he t.

ed with 3 parts of benzoyl chloride in 100 parts of nitrobenzene for one hour at reflux temperature. The mass is cooled and the crystalline product is isolated by filtration, washed with nitrobenzene and then with alcohol and dried. It is a dark red powder soluble in hot organic solvent with a red color and in concentrated sulfuric acid with a reddish brown color. It dyes cotton from a violet vat in red shades.

When the dibromo-3-amino-anthraquinone- 2,1(N) -benzacridone is replaced by a trichlorinated 3-amino-anthraquinone-2,1(N) benzacridone, dyestufis having similar properties to those obtained in Example 4 are obtained.

It is, of course, understood that other acid chlorides than those specifically mentioned above may be condensed with 3-amino-anthraquinone-2,1(N) -benzacridone to produce dyestuffs having similar properties. Di-acid chlorides, for example diphenyl dicarboxylic acid chlorides,

etc., and the long chain fatty acid chlorides, may

be employed.

As illustrated above the halogenated derivatives can be prepared by direct halogenation of the condensation product or by using as the starting material a halogen containing S-aminoanthraquinone-2,1(N) -benzacridone. The halogenation of the condensation product may be carried out in sulfuric acid, organic solvents, hydrochloric acid, or aqueous suspension. The addition of halogen to the molecule, irrespective of the constitution of the acidylamino group, imparts to the dyestufi increased tinctorial strength.

I claim:

1. Compounds of the class consisting of those of the following general formula and their halogenation products wherein R stands for an acyl radical of an organic carboxylic acid.

2. Compounds of the following general formula wherein R stands for an acyl radical of an organic carboxylic acid.

3. Compounds of the following general formula wherein R stands for an acyl radical of an organic carboxylic acid of the benzene series.

WILLIAM DET'I'WYLER. 

